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Experimental and theoretical study of the UV-Vis

spectrum of a new coumarine-derived ligand

Dejan Milenković1*, Srećko Trifunović2, Edina Avdović2, Nenad Vuković2, Milena

Vukić2, Jasmina Dimitrić-Marković3, and Zoran Marković1,4

1Bioengineering Research and Development Center, Prvoslava Stojanovića 6, 34000

Kragujevac, Serbia 2Faculty of Science, University of Kragujevac, 12 Radoja Domanovića, P.O. Box 60, 34000

Kragujevac, Serbia 3Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12-16,11000

Belgrade, Republic of Serbia 4Department of Chemical-Technological Sciences, State University of Novi Pazar, Vuka

Karadžića bb, 36300 Novi Pazar, Serbia

Abstract. The UV-Vis properties of new coumarine-derived ligand (3-(1-(3-

hydroxypropylamino)propylidene)-chroman-2,4-dione) were investigated. The

time-dependent density functional theory (TDDFT) approach in combination

with the B3LYP functional was used for simulation of UV-Vis spectra of

examined compound. The agreement between the observed wavelengths and

intensities in the UV spectrum of ligand 1 and those predicted with B3LYP

functional, is satisfactory.

Keywords: UV-Vis spectra, TDDFT, B3LYP, coumarine-derived ligand

(ligand 1), oscillator strengths

1 Introduction

Coumarins (2H-1-benzopyran-2-one) consist of a large class of phenolic substances

found in plants and are made of fused benzene and 𝛼-pyrone rings [1]. Coumarine and

its derivatives are natural compounds with high and significant bilogical activities like

spasmolitic, antiarrhytmic, cardiotonic and photodynamic properties [2]. Аlso,

coumarine and its derivatives were tested against several tumor cell lines [3]. These

compounds can be found in different food sources such as fruits, herbs and

vegetables [4]. Coumarin and its derivatives have important role in the fields of

biology, medicine, industry, botany and chemistry. Some metal complexes with

coumarine derivatives showed significant anticoagulant [5] and antitumor activity

[2,6].

* Dejan Milenković, Bioengineering Research and Development Center, Prvoslava Stojanovića

6, 34000 Kragujevac, Serbia ([email protected])

2 Methodology section

The equilibrium geometry of coumarine-derived ligand (1) was optimized by density

functional theory (DFT) using B3LYP exchange correlation functional first proposed

by Becke [7], in combination with the 6–311+G(d,p) basis set. The optimization was

carried out using Gaussian 09 package [8]. The structure was optimized at 298 K

without any geometrical restrictions. The nature of the stationary points was

determined by performing frequency analysis: equilibrium geometries have no

imaginary vibrations. The effect of methanol as solvent was taken into account in

geometry optimization and energy calculation by using the SMD model [9].

To simulate the UV spectrum of investigated compound TDDFT (Time Dependent

Density Functional Theory) approach [10] was employed for predicting the electronic

transitions. TD calculation was performed in methanol. All transitions were

considered. All parameters important for the simulation of UV-VIS spectra such as

excited state energies, oscillator strengths (f), and a list of the transitions that gave rise

to each excited state were calculated. Natural Bond orbital (NBO) analysis [11] was

performed for the explanation of the interactions inside of molecule and visualization

of orbitals involved in electronic transitions. The B3LYP ground state geometry was

used to perform the NBO.

3 Results and discussion

3.1 Structural analysis

The structure of most stable conformation of ligand 1 defined by using B3LYP

local density functional method in conjunction with 6–311+G(d,p) basis set, in

methanol as solvent. From the optimized molecular structure of the ligand 1 (Fig. 1),

it is found that torsion angle, τ, defined by the C4–C3–C1'–N1 atoms is 172°, which

indicated nonplanarity of molecule. The investigated molecule has one internal

hydrogen bond (IHB) which additionally stabilize corresponding compound. For this

IHB the NBO analysis revealed that electron density is donated from the p and sp2

orbitals of the oxygen atoms into the proximate σ* antibonding H–N1 bond. These

donor-acceptor interactions are responsible for hydrogen bond formation.

Figure 1. Optimized geometry of the ligand 1 obtained at the B3LYP/6-311+G(d,p) level of

theory in methanol.

3.2 UV spectrum

The experimental and computed UV spectra are presented in Fig. 2, whereas

calculated electronic transitions, absorption wavelengths, and oscillator strength, as

well as experimental absorption wavelengths are presented in Table 1.

Table 1. UV spectral data for compound 1.

Expt B3LYP/6-311+G(d,p)

λmax (nm) λmax f Orbital description

319 294 0.52 H → L (66%)

243 248 0.18 H → L+1 (48%)

234 238 0.28 H-1→ L+1 (58%)

The experimental spectrum of 1 in of methanol shows two wide peaks at 319 and 243

nm. The theoretical investigation of electronic transition was also performed in

methanol. The UV spectrum of the compound 1 was simulated using the TDDFT

approach. In Table 1 are given data for the UV spectrum. The two absorption peaks

are prominent, i.e., at 294 nm which is absorption maximum and the second peak has

been observed at 248 nm which are in good agreement with the experimental

evidences (Table 1, Fig. 2). As mentioned above, electronic transitions have been

investigated. The first transition state at 294 nm dominated with maximum absorption

which is caused by HOMO →LUMO with 66% contribution. The second transition

state caused by HOMO → LUMO+1 at 248 nm with 48% contribution. The third

state has 58% contribution from HOMO-1 → LUMO+1. The orbitals cooresponding

for these electronic transitions were presenred in Fig. 3.

Figure 2. Experimental (blue line) and simulated (red line) UV spectrum of ligand 1 in

methanol. The calculation of the spectrum was carried out at the B3LYP-D3/6-311+G(d,p)

level of theory in combination with the SMD solvation model.

Figure 3. The occupied and virtual orbitals responsible for the UV spectrum of ligand 1.

The shapes of the corresponding orbitals confirm that these transitions were

associated with significant charge transfer between the coumarine moiety and side

alkyl chain.

4 Conclusion

All results were obtained using the B3LYP/6-311+G(d,p) level of theory. On the basis

of conformational analysis, it was found that 1 is the most stable structure. Re-

optimized structure of 1 in methanol was used to simulate the UV–vis spectra. Both

methods, experimental and theoretical showed as two major peaks. The results

showed that there is good agreement between experimental and calculated values for

λmax. On the basis of new facts, it is clear that this functional (B3LYP) can be used

successfully in the study of this class of compounds. According to the analysis of

frontier orbitals it was found that for these transitions was responsible charge transfer

between the coumarine moiety and side alkyl chain.

Acknowledgments. This work was supported by the Ministry of Science of the

Republic of Serbia (Projects Nos. 172015, 174028 and 172016).

References

1. Aoyama, Y., Katayama, T., Yamamoto, M., Tanaka, H., Kon, K.: A new antitumor

antibiotic product, demethylchartreusin. Isolation and biological activities. J. Antibiot. 45,

875-888 (1992)

2. Manolov, I., Kostova, I., Netzeva, T., Konstantinov, S., Karaivanova, M.: Cytotoxic

activity of cerium complexes with coumarin derivatives. Molecular modeling of the ligands.

Arch. Pharm. (Weinheim) 333, 93–98 (2000).

3. Weber, U.S., Steffen, B., Siegers, C.: Antitumor-activities of coumarin, 7- hydroxy-coumarin

and its glucuronide in several human tumor cell lines. Res. Commun. Mol. Pathol.

Pharmacol. 99, 193-206 (1998)

4. Kleiner, H.E., Vulimiri, S.V., Miller, L., Johnson, W.H. Whitman, C.P., DiGiovanni, J.: Oral

administration of naturally occurring coumarins leads to altered phase I and II enzyme

activities and reduced DNA adduct formation by polycyclic aromatic hydrocarbons in

various tissues of SENCAR mice. Carcinogenesis. 22, 73-82 (2001).

5. Jiang, D., Deng, R., Wu, J.: Synthesis and properties of lanthanide compounds of 3-sulfo-4-

hy-droxycoumarin. Wuji Huaxue. 5, 21–28 (1989)

6. Kostova, I., Manolov, I., Konstantinov, S., Karaivanova, M.: Synthesis, physicochemical

characterisation and cytotoxic screening of new complexes of cerium, lanthanum and

neodymium with Warfarin and Coumachlor sodium salts. Eur. J. Med. Chem. 34, 63–68

(1999)

7. Becke, A.D.: Density-functional exchange-energy approximation with correct asymptotic

behavior. Phys. Rev. A Gen. Phys. 38, 3098-3100 (1988)

8. Frisch, M. J., Trucks, G. W., Schlegel, H. B., et al. Gaussian 09, revision A.1-

SMP.Wallingford, CT: Gaussian, Inc. (2009).

9. Marenich, A.V., Cramer, C.J. Truhlar, D.G.: Universal solvation model based on solute

electron density and on a continuum model of the solvent defined by the bulk dielectric

constant and atomic surface tensions. J. Phys. Chem. B 113, 6378-6396 (2009)

10. Bauernschmitt, R., Ahlrichs, R.: Treatment of electronic excitations within the adiabatic

approximation of time dependentdensity functional theory. Chem. Phys. Lett. 256, 454-464

(1996)

11. Foster, J.P., Weinhold, F.: Natural hybrid orbitals. J. Am. Chem. Soc. 102, 7211–7218

(1980)

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